CN1393496A - 阴极涂料分散液 - Google Patents
阴极涂料分散液 Download PDFInfo
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- CN1393496A CN1393496A CN02124863A CN02124863A CN1393496A CN 1393496 A CN1393496 A CN 1393496A CN 02124863 A CN02124863 A CN 02124863A CN 02124863 A CN02124863 A CN 02124863A CN 1393496 A CN1393496 A CN 1393496A
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- dispersing liquid
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- 239000011248 coating agent Substances 0.000 title claims abstract description 58
- 238000000576 coating method Methods 0.000 title claims abstract description 58
- 239000007788 liquid Substances 0.000 title claims description 75
- 239000006185 dispersion Substances 0.000 claims abstract description 54
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000004593 Epoxy Substances 0.000 claims abstract description 20
- 239000011230 binding agent Substances 0.000 claims abstract description 19
- 239000006229 carbon black Substances 0.000 claims abstract description 19
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims abstract description 18
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 17
- 239000010439 graphite Substances 0.000 claims abstract description 17
- 229920000877 Melamine resin Polymers 0.000 claims abstract description 15
- 239000000203 mixture Substances 0.000 claims abstract description 15
- 150000002148 esters Chemical class 0.000 claims abstract description 11
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229920000459 Nitrile rubber Polymers 0.000 claims abstract description 8
- NTXGQCSETZTARF-UHFFFAOYSA-N buta-1,3-diene;prop-2-enenitrile Chemical compound C=CC=C.C=CC#N NTXGQCSETZTARF-UHFFFAOYSA-N 0.000 claims abstract description 8
- 150000001718 carbodiimides Chemical class 0.000 claims abstract description 8
- 238000004132 cross linking Methods 0.000 claims abstract description 8
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- 239000003377 acid catalyst Substances 0.000 claims abstract description 6
- 229920001909 styrene-acrylic polymer Polymers 0.000 claims abstract description 3
- 239000003795 chemical substances by application Substances 0.000 claims description 28
- 230000001681 protective effect Effects 0.000 claims description 16
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- 239000002518 antifoaming agent Substances 0.000 claims description 8
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- 238000007711 solidification Methods 0.000 claims description 7
- 230000008023 solidification Effects 0.000 claims description 7
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 6
- 239000013543 active substance Substances 0.000 claims description 5
- -1 sanitas Substances 0.000 claims description 5
- 239000000080 wetting agent Substances 0.000 claims description 5
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 claims description 4
- 229920000178 Acrylic resin Polymers 0.000 claims description 3
- 239000004925 Acrylic resin Substances 0.000 claims description 3
- 239000002174 Styrene-butadiene Substances 0.000 claims description 3
- 239000012528 membrane Substances 0.000 claims description 3
- 239000011115 styrene butadiene Substances 0.000 claims description 3
- 229920003048 styrene butadiene rubber Polymers 0.000 claims description 3
- CJMZLCRLBNZJQR-UHFFFAOYSA-N ethyl 2-amino-4-(4-fluorophenyl)thiophene-3-carboxylate Chemical compound CCOC(=O)C1=C(N)SC=C1C1=CC=C(F)C=C1 CJMZLCRLBNZJQR-UHFFFAOYSA-N 0.000 claims description 2
- 150000007974 melamines Chemical class 0.000 claims description 2
- 238000003892 spreading Methods 0.000 claims description 2
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims 2
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims 2
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims 1
- 230000015572 biosynthetic process Effects 0.000 claims 1
- 239000004575 stone Substances 0.000 claims 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 11
- 239000003513 alkali Substances 0.000 abstract description 2
- 239000004971 Cross linker Substances 0.000 abstract 1
- 238000009472 formulation Methods 0.000 abstract 1
- 238000004519 manufacturing process Methods 0.000 abstract 1
- 238000005580 one pot reaction Methods 0.000 abstract 1
- 229920001187 thermosetting polymer Polymers 0.000 abstract 1
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 18
- 239000000126 substance Substances 0.000 description 9
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 6
- 229910000831 Steel Inorganic materials 0.000 description 6
- 239000010959 steel Substances 0.000 description 6
- UEEJHVSXFDXPFK-UHFFFAOYSA-N N-dimethylaminoethanol Chemical compound CN(C)CCO UEEJHVSXFDXPFK-UHFFFAOYSA-N 0.000 description 5
- 239000000654 additive Substances 0.000 description 5
- 230000000996 additive effect Effects 0.000 description 5
- 238000005260 corrosion Methods 0.000 description 5
- 230000007797 corrosion Effects 0.000 description 5
- 238000005115 demineralization Methods 0.000 description 5
- 230000002328 demineralizing effect Effects 0.000 description 5
- 239000012972 dimethylethanolamine Substances 0.000 description 5
- NIXOWILDQLNWCW-UHFFFAOYSA-N Acrylic acid Chemical compound OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 4
- 229910021383 artificial graphite Inorganic materials 0.000 description 4
- 239000001913 cellulose Substances 0.000 description 4
- 229920002678 cellulose Polymers 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 229920003270 Cymel® Polymers 0.000 description 3
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 3
- 229960002887 deanol Drugs 0.000 description 3
- 229920000126 latex Polymers 0.000 description 3
- 239000004816 latex Substances 0.000 description 3
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- 239000002245 particle Substances 0.000 description 3
- 238000007789 sealing Methods 0.000 description 3
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 3
- 229940117958 vinyl acetate Drugs 0.000 description 3
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 2
- 206010013786 Dry skin Diseases 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 2
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 2
- UREZNYTWGJKWBI-UHFFFAOYSA-M benzethonium chloride Chemical compound [Cl-].C1=CC(C(C)(C)CC(C)(C)C)=CC=C1OCCOCC[N+](C)(C)CC1=CC=CC=C1 UREZNYTWGJKWBI-UHFFFAOYSA-M 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000000839 emulsion Substances 0.000 description 2
- 238000007747 plating Methods 0.000 description 2
- 229920002857 polybutadiene Polymers 0.000 description 2
- KBPLFHHGFOOTCA-UHFFFAOYSA-N 1-Octanol Chemical compound CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 description 1
- PZOGAKOZVSTZSO-UHFFFAOYSA-N 2-methyl-5,6-dihydro-4h-cyclopenta[d][1,2]thiazol-3-one Chemical compound C1CCC2=C1SN(C)C2=O PZOGAKOZVSTZSO-UHFFFAOYSA-N 0.000 description 1
- GUQMDNQYMMRJPY-UHFFFAOYSA-N 4,4-dimethyl-1,3-oxazolidine Chemical compound CC1(C)COCN1 GUQMDNQYMMRJPY-UHFFFAOYSA-N 0.000 description 1
- CFKMVGJGLGKFKI-UHFFFAOYSA-N 4-chloro-m-cresol Chemical compound CC1=CC(O)=CC=C1Cl CFKMVGJGLGKFKI-UHFFFAOYSA-N 0.000 description 1
- QYYMDNHUJFIDDQ-UHFFFAOYSA-N 5-chloro-2-methyl-1,2-thiazol-3-one;2-methyl-1,2-thiazol-3-one Chemical compound CN1SC=CC1=O.CN1SC(Cl)=CC1=O QYYMDNHUJFIDDQ-UHFFFAOYSA-N 0.000 description 1
- XUTDJVFRVABGQY-UHFFFAOYSA-M 76902-90-4 Chemical compound [Cl-].C1N(C2)CN3CN2C[N+]1(C)C3 XUTDJVFRVABGQY-UHFFFAOYSA-M 0.000 description 1
- 241000640882 Condea Species 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 229920001213 Polysorbate 20 Polymers 0.000 description 1
- 229920013804 TRITON CF-32 Polymers 0.000 description 1
- 229920013624 Tylac Polymers 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000002390 adhesive tape Substances 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 229920003232 aliphatic polyester Polymers 0.000 description 1
- 230000029936 alkylation Effects 0.000 description 1
- 238000005804 alkylation reaction Methods 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 230000001458 anti-acid effect Effects 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- PVEOYINWKBTPIZ-UHFFFAOYSA-N but-3-enoic acid Chemical compound OC(=O)CC=C PVEOYINWKBTPIZ-UHFFFAOYSA-N 0.000 description 1
- 239000003990 capacitor Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 239000002612 dispersion medium Substances 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 229920002313 fluoropolymer Polymers 0.000 description 1
- 239000004811 fluoropolymer Substances 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910021382 natural graphite Inorganic materials 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 229920001692 polycarbonate urethane Polymers 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 239000000256 polyoxyethylene sorbitan monolaurate Substances 0.000 description 1
- 235000010486 polyoxyethylene sorbitan monolaurate Nutrition 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- TVPFLPJBESCUKI-UHFFFAOYSA-M potassium;n,n-dimethylcarbamodithioate Chemical compound [K+].CN(C)C([S-])=S TVPFLPJBESCUKI-UHFFFAOYSA-M 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 229920005792 styrene-acrylic resin Polymers 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/02—Emulsion paints including aerosols
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/02—Details
- H01M8/0202—Collectors; Separators, e.g. bipolar separators; Interconnectors
- H01M8/0204—Non-porous and characterised by the material
- H01M8/0223—Composites
- H01M8/0226—Composites in the form of mixtures
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/24—Electrically-conducting paints
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
- H01G9/004—Details
- H01G9/04—Electrodes or formation of dielectric layers thereon
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- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/60—Selection of substances as active materials, active masses, active liquids of organic compounds
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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- H—ELECTRICITY
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- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
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- H01M50/124—Primary casings; Jackets or wrappings characterised by the material having a layered structure
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/10—Primary casings; Jackets or wrappings
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- H01M50/133—Thickness
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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- H01M8/0204—Non-porous and characterised by the material
- H01M8/0213—Gas-impermeable carbon-containing materials
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- H—ELECTRICITY
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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- Y02E60/13—Energy storage using capacitors
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
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- Cell Electrode Carriers And Collectors (AREA)
- Fuel Cell (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Sealing Battery Cases Or Jackets (AREA)
- Inert Electrodes (AREA)
- Electric Double-Layer Capacitors Or The Like (AREA)
- Solid Thermionic Cathode (AREA)
- Primary Cells (AREA)
Abstract
本发明涉及含石墨及/或炭黑的适用于电池生产的阴极涂料分散液。此分散液如敷涂于阴极表面,可使之耐水和耐碱,并且还导电。该分散液乃一基于水的热固性单容器配制体系,含有至少两种粘结剂,它们是环氧酯和苯乙烯丙烯酯脂、苯乙烯丁二烯或丁二烯丙烯腈。含丁二烯丙烯腈的配方还适合用作耐酸涂料。本分散液还含有至少一种交联剂,如蜜胺及/或碳二亚胺。在分散液中使用酸催化剂可使交联加速进行。
Description
发明领域
本发明涉及单容器配制的高温热固性阴极涂料分散液。其配方含有石墨及/或炭黑,丙烯酸树脂或丁二烯丙烯腈或苯乙烯丁二烯或环氧树脂及/或环氧酯。对该涂料用恰当的交联剂,如蜜胺及/或酚醛树脂及/或碳二亚胺,和酸催化剂来固化。这些涂料适用于电池、电容器和其它储能装置。
发明背景
碱性干电池通过预成型内壁镀镍的密封钢管壳来制造。电池的阴极为二氧化锰、碳以及其它可能添加剂的压缩混合物,它以中空圆筒的形状置于密封钢管壳内,和该钢管壳内表面有紧密的接触。另一方面,可以在电池外形成阴极材料环,然后再将其推入密封钠管壳中。为了改善密封钢管壳和阴极混合物的电接触并防止镍层和管壳受到电解质的腐蚀,可以在管壳的内表面与阴极混合物之间,浇注一种导电的分散液,对管壳的内壁进行处理。
过去已使用过各种乳胶剂,以图使电接触最佳化并防止电池中的腐蚀。这些乳胶剂一般含有石墨及/或炭黑,联同一种粘结剂。例如,美国4810600号专利利用一种含石墨及/或炭黑的分散液,联同一种粘结剂,其为a)乙烯基乙酸酯和乙烯,b)乙烯基乙酸酯和氯乙烯,c)苯乙烯和丁二烯,或d)乙烯基乙酸酯、氯乙烯和乙烯。此外,含芳香族聚氨酯、苯乙烯丙烯酸、脂肪族聚酯聚氨酯、乙烯基醋酸脂丙烯酸、脂肪族聚碳酸酯尿烷和含氟聚合物粘结剂的其它分散液也已被利用。所有以上的分散液,可当作一种热塑性塑料加以使用,以处置时无需交联剂。在最终完成对镀镍钢的处理之后,当经受高浓度的氢氧化钾时,这些不同的分散液全都呈现出某些形式的缺陷。在一些个案中,KOH试验后分散液的电阻相对于试验前要高,而在一些个案中,当将分散液喷涂于镀镍极上,在80℃干燥20分钟,然后再浸泡于40%的KOH溶液中,在80℃保持72小时时,则其粘结剂便或者变软,或者失去粘性。粘结剂软化的一个主要原因是其较低的Tg(玻璃转化温度)。可以凭借同其它树脂的交联反应得到更硬的涂料,它们要有更高的Tg,且在更高的温度下将不软化。
本发明的目的是,提供一种组合成的、热激活交联的导电涂料,供在电池、燃料电池、电容器或其它储能装置中应用。此涂料分散液由石墨及/或炭黑、粘结剂、交联剂和一种催化剂制成。涂料形成稳定的导电阴极层,它本身又改善了该能量装置的储存和释放特性。这一涂料的改进的特性还包括,当它经受氢氧化钾和升高的温度时,仍对阴极表面有强的附着力。本发明的另外的目的还在提供一种分散液,它可用于燃料电池的双极板或超级电容器中作为电极集电器。
发明概述
本分散液为包括苯乙烯丙烯酸和环氧树酯的单容器配制体系,其中加入了蜜胺及/或碳二亚胺作为交联剂。此配方中也可以含有一种嵌段酸,以催化交联反应。通过使用丁二烯丙烯腈或苯乙烯丁二烯和环氧酯,并包括以上的交联剂和催化剂,也可配制成一种类似的分散液。此外,分散液也可由环氧树脂及/或环氧酯和酸催化剂、作为交联剂的酚醛树脂及/或蜜胺所组成。这些单容器配制体系,当应用于镀镍钢时,呈现出在较高温度下甚佳的抗碱性,并形成好的导电性。含丁二烯丙烯腈的配方还显示出好的抗酸性。所以,这些涂料可用作诸如碱性电池等储能装置的阴极涂料,它在碱电池、燃料电池、电容器和其它储能装置中,除对化学品具有极好的抗蚀性外,还产生合适的导电性。
发明详述
本发明的分散液包括石墨及/或炭黑,以及至少两种含有用于交联反应的羧基功能的树脂。同样地使用环氧和酚醛树脂及/或蜜胺也可配制成一种第二类分散液。环氧树脂的羟基同蜜胺交联,而环氧基同酚醛树脂交联。交联反应仅在升高温度一定时间后才会发生。交联反应生成非常耐碱和耐酸的涂层,并产生一个好的导电层。
石墨分散液乃专门为碱性电池的阴极集电器而开发。这种分散液用作集电器的涂料,并防止碱电池内腐蚀性的化学环境对电极的腐蚀。该分散液,尤其是含丁二烯丙烯腈或环氧树脂作为粘结剂的配方,不仅抗碱,而且还抗酸。所以,此涂料也可用于燃料电池,在燃料电池中,具有较高电阻的集电器涂层对于双极电极而言,是人们所企求的。
这些分散液主要用于敷涂阴极支座或电池的密封管壳。同样,这些分散液也适合用作超级电容器电极上的集电器涂料。这些涂料形成联接层,改善电极与电解质之间的电接触,电解质从本质上讲可为含水的或不含水的。用于此分散液中的优选石墨为高纯度的高结晶度的天然或合成石墨。在分散液混合物中,按约30-90%固体总重的用量使用导电石墨。为制备适当的分散液,要利用去矿化水作分散介质。为获得无问题的涂料,还需加入下列的添加剂。例如,去沫剂、防腐剂、表面活性剂及/或分散剂都可利用。可利用的去沫剂包括BYK 022、BYK019、BYK 24(BYK化学公司)、DF 37、DF 40、DF 120、DF 70、DF 75、DF 58、DF 60、DF 62、DF 66、DF 574、DF 696(空气产品及化学品公司)、Nalco 2300、Nalco 2305、Nalco 2302(罗恩哈斯公司)、Triton CF-32(BASF公司)、L-62(Witco)、Coatsil 1300(Condea Vista)和Alfol 8醇。可利用的防腐剂包括Busan 85、Busan 2024、Busan 1024(贝克曼实验室)、Hyamine 10-X、Hyamine 2389(罗恩哈斯公司)、Promexal X50(Zeneca)、Parmetol DF 18(S & M特殊添加剂公司)、Kathon 886(罗恩哈斯公司)和Nuosept 101(Creanova)。可利用的分散剂包括Busperse 229(贝克曼实验室)、Tamol N、Tamol 731、Tamol 850、Tamol SN(罗恩哈斯公司)、Daxad 30-30、Daxad 11、Daxad 15、Daxad 19(W & R Grace公司)、CT 136、CT 141、CT 151、CT 161、CT 171(空气产品和化学品公司)、Disperbyk 182、Disperbyk190和Disperbyk 185(BYK化学公司)。可运用的润湿剂包括Tween 20(光谱级产品公司)、Orotan和Silwet L-7068(Witco)。可利用的表面活性剂包括104A、104B、104DPM、104E、104H、104NP、104PA(空气产品和化学品公司)和BYK 333。
在优选的实施方案中,添加剂约占配方用料总重量的0.01-5%。在尤其优选的实施方案中,还可以在配料混合物中加入润湿剂。
为了形成合适的树脂分散液,要使石墨及/或炭黑同丙烯酸乳胶和环氧酯混合。这里所用的丙烯酸乳胶含有粘结剂体系的聚合骨架中的苯乙烯和丙烯酸或丁二烯树脂。环氧酯最好具有为10-100的酸值。丙烯酸树脂对苯乙烯或丁二烯树脂的比率最好约为0.01∶9。同样地可以制得同样用途的第二种分散液,它含有石墨及/或炭黑,以及丁二烯丙烯腈和环氧酯。所有上面提到的粘结剂均含羧基的功能,为提供与蜜胺及/或碳二亚胺的交联反应。第三种分散液由含有环氧树脂和环氧酯的石墨及/或炭黑制得。此外,分散液也含有作为交联剂的蜜胺和酚醛树脂。对于指望的用途来说,为达到适当的导电性,需要以合适的石墨及/或炭黑对粘结剂的比率来制备混合物。例如,为供电池密封管壳所用,石墨及/或炭黑对粘结剂的合适比率约为1∶6,优选的比率约为1∶4。分散液水的总含量最好约占重量的30-90%,而石墨及/或炭黑混合物最好约为总干重量的10-60%。
在适当的添加剂和粘结剂存在的情况下,可制成一种稳定的分散液。其粘度介于50mPa.sec和1200mPa.sec之间。为适当固化起见,该分散液还含有一种或多种交联剂以及一种酸催化剂。优选交联剂为蜜胺、碳二亚胺、酚醛树脂或其混合物。酸催化剂可用来催化蜜胺与粘结剂的反应。可以利用一种固化剂,它包括蜜胺以及最好是带有较高级亚胺基的部分烷基化的蜜胺。
优选的交联剂包括完全或部分烷基化蜜胺。可能得到的交联剂包括C-327、C-324、C-325、C-1158、C-323、C-303、C-350、C-370、C-385、C-1123(CYTEC)和Ucarlink XL 29SE(联合碳化物公司)。
功能羧基与蜜胺的反应,可用各类磺酸包括嵌段磺酸来催化。更具体地说对甲苯磺酸的胺盐(p-TSA),诸如BYK催化剂450、BYK催化剂460(BYK化学公司)、Nacure 2107与Nacure 2500、Nacure49-110(King Industries,Inc.),或环氧嵌段二壬基萘磺酸,诸如Nacure1419(King Industries,Inc.)、Cycat 296-9催化剂(Cytec)或Nacure49-110。
优选的酚醛树脂包括Phenodur PR 308、Phenodur PR 307和Phenodur VPW 1942/52 WA(Solutia)。
涂料在制好后,可通过浇、刷、喷或浸将其敷涂到处理的表面上,并在升高温度下加以固化。水分可借助加温或应用真空,使其干燥而去除。优选的固化处理温度约为100℃-250℃。处理的时间从15秒至16分钟不等,视所选的固化处理方法而定。固化处理的速率能通过改变交联剂和催化剂的用量来控制。固化后,在处理的表面上便留下一层有耐机械和化学性、电解质不可溶的保护膜。所形成的涂层的比电阻约为5-100欧姆/平方。该分散液所形成的保护涂层暴露于80℃ 40%的KOH溶液72小时后,其电阻不大于其初始值的两倍。涂料的施用量可加以选择,使得水蒸掉后所形成的保护膜的厚度优选地约为5-200微米,最优选地约为20-100微米。借助于分散液的准塑性和触变性,可以得到均匀的厚度。
参考下列实例可便于对本发明的更好理解,这些实例意在用来说明解释,并非以任何方式对本发明范围加以限定。
实施例
两种配方的分散液可按下列步骤制备。
1.将90%去矿化水、分散剂和纤维素装入环形研磨机。搅拌5-10分钟或直至溶解。
2.加入去沫剂、炭黑和石墨粉。
3.旋转研磨机5小时或直至达到为5.0的最小Hegman。
4.对卸出配料作如下处理:预先混合环氧酯和DMEA,然后再加入配料中,使之混合10分钟。然后加入乳胶和蜜胺及/或碳二亚胺,并使之混合15-20分钟。加入催化剂前,将配料温度调节至约为32℃-35℃,然后再加入催化剂。配料粘度用水来调节,而pH用DMEA及/或氨水来调节。实施例1和实施例2列出了每种配方的组分。
实施例1
炭黑(Vulcan XC-72颗粒) 3.030克
纤维素 0.69
二甲基乙醇胺 0.31
去沫剂 0.16
分散剂 0.77
去矿化水 49.92
合成石墨(39号石墨粉) 20.63
Chempol 010-0453 2.470
Neocryl A-662 17.28
Cymel 323 4.63
Nacure X49-110 0.25
100克
实施例2
炭黑(Vulcan XC-72颗粒) 3.030克
纤维素 0.69
二甲基乙醇胺 0.25
去沫剂 0.16
分散剂 0.77
去矿化水 45.64
合成石墨(39号石墨粉) 20.63
Chempol 010-0453 2.470
Tylac 97767 22.74
Cymel 323 3.86
Nacure X49-110 0.25
XL 29SE 1.23
100克
实施例3
炭黑(Vulcan XC-72颗粒) 3.030克
纤维素 0.69
二甲基乙醇胺 0.48
去沫剂 0.16
分散剂 0.77
去矿化水 53.07
合成石墨(39号石墨粉) 20.63
Chempol 010-0453 2.470
Phenodur VPW 1942/52WA 13.82
Cymel 323 4.63
Nacure X49-110 0.25
100克
将由实例1和实例2制得的涂料喷涂于镀镍板上,并在150℃固化处理3分钟或在205℃固化处理1分钟。实例3的涂料则在205℃烘烤3分钟。然后把该镀镍板放入40%的KOH溶液中,在80℃保持72小时。尔后从溶液中取出该板,用流动水洗涤,再放到烘箱内在60℃干燥30分钟。进行了一种胶带试验,其中把Scotch牌胶带牢牢地压贴到每个样品上,然后再以90度角缓缓地除去。每个样品所呈现出的极好的粘着力就在于,无一样品的涂层会通过这样的胶带试验而被除去。
尽管本发明在描述时特别提到其中的某些实施方案,但是,应当理解,在下列权利要求的精神和范围内,有普通技能的人做出改动和修正也是可能的。
Claims (29)
1.一种供敷涂储能装置之用的涂料分散液,包含石墨、炭黑或其混合物、粘结剂和一种或多种交联剂,其中所述的涂料分散液以均相含水分散液施加,它所述储能装置上形成一层保护膜,且其中的粘结剂选自苯乙烯丙烯酸、丁二烯丙烯腈、丁二烯苯乙烯、环氧树脂和环氧酯。
2.权利要求1中的涂料分散液,其中的交联反应剂包括蜜胺、碳二亚胺、酚醛树脂和酸催化剂或其混合物。
3.权利要求1中的涂料分散液,其中石墨、炭黑或其混合物对粘结剂的比率约为1∶6。
4.权利要求3中的涂料分散液,其中石黑、炭黑或其混合物对粘结剂的比率约为1∶4。
5.权利要求3中的涂料分散液,其中分散液的水含量约为30-90重量%。
6.权利要求5中的涂料分散液,其中石墨、炭黑或其混合物的干物质重量约为10-60重量%。
7.权利要求3中的涂料分散液,其中分散液另外还含有一种或多种去沫剂、防腐剂、分散剂、润湿剂、表面活性剂或其混合物。
8.权利要求7中的涂料分散液,其中一种或多种去沫剂、防腐剂、分散剂、润湿剂、表面活性剂或其混合物约占0.05-5重量%。
9.权利要求8中的涂料分散液,其中分散液含有约0.05-5重量%的润湿剂。
10.权利要求7中的涂料分散液,其中分散液含有约0.05-5重量%的表面活性剂。
11.权利要求6中的涂料分散液,其中固化处理剂为部分烷基化的具有较高级亚胺基的蜜胺。
12.权利要求10中的涂料分散液,其中包含约0-5重量%的第二交联剂。
13.权利要求12中的涂料分散液,其中第二交联剂为碳二亚胺。
14.权利要求11中的涂料分散液,其中还含有选自对甲苯磺酸胺盐、环氧嵌段的二壬基萘磺酸或其混合物的一种催化剂。
15.权利要求14中的涂料分散液,其中分散液的粘度约为50-1200cps。
16.权利要求15中的涂料分散液,其中粘结剂含有一种酸值为10-100的环氧酯。
17.权利要求15中的涂料分散液,其中分散液含有苯乙烯和丙烯,苯乙烯对丙烯的比率约为0.1∶9。
18.权利要求15中的涂料分散液,其中分散液含有苯乙烯丁二烯树脂和丙烯酸树脂,苯乙烯对丁二烯的比率约为0.1∶9。
19.权利要求15中的涂料分散液,其中分散液含有丁二烯和丙烯腈,两者的比率约为0.01∶9。
20.权利要求13的涂料分散液,其可在约为100℃至250℃的温度范围内,受到约15秒到16分钟的固化处理。
21.权利要求1中的涂料分散液,其中分散液形成一种电导率约为5-100欧姆/平方的保护膜。
22.权利要求1中的涂料分散液,其中涂料分散液形成的防护膜在暴露于80℃ 40%KOH溶液72个小时后,其电阻不大于其初始值的两倍。
23.权利要求1中的涂料分散液,其中储能装置为电池、燃料电池或电容器。
24.含有由权利要求1中的涂料分散液淀积而成的导电保护膜的储能装置,其中所述导电保护膜的厚度约为5-200微米。
25.含有由权利要求1中的涂料分散液淀积而成的导电保护膜的碱性电池,其中所述导电保护膜的厚度约为20-100微米。
26.含有由权利要求1中的涂料分散液淀积而成的导电保护膜的燃料电池,其中所述导电保护膜的厚度约为5-200微米。
27.含有由权利要求1中的涂料分散液淀积而成的导电保护膜的燃料电池,其中所述导电保护膜的厚度约为20-100微米。
28.含有由权利要求1中的涂料分散液淀积而成的导电保护膜的电容器,其中所述导电保护膜的厚度约为5-200微米。
29.含有由权利要求1中的涂料分散液淀积而成的导电保护膜的电容器,其中所述导电保护膜的厚度约为20-100微米。
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---|---|---|---|
US09/888,306 US20030008209A1 (en) | 2001-06-22 | 2001-06-22 | Cathode coating dispersion |
US09/888306 | 2001-06-22 |
Publications (1)
Publication Number | Publication Date |
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CN1393496A true CN1393496A (zh) | 2003-01-29 |
Family
ID=25392950
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN02124863A Pending CN1393496A (zh) | 2001-06-22 | 2002-06-21 | 阴极涂料分散液 |
Country Status (9)
Country | Link |
---|---|
US (1) | US20030008209A1 (zh) |
EP (1) | EP1271671B1 (zh) |
JP (1) | JP4779066B2 (zh) |
KR (1) | KR20030001263A (zh) |
CN (1) | CN1393496A (zh) |
AT (1) | ATE529905T1 (zh) |
CA (1) | CA2390804C (zh) |
PT (1) | PT1271671E (zh) |
SG (1) | SG106074A1 (zh) |
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CN104247112A (zh) * | 2012-04-13 | 2014-12-24 | 株式会社Uacj | 集电体、电极结构体、非水电解质电池及蓄电零部件 |
CN105255287A (zh) * | 2015-11-20 | 2016-01-20 | 苏州菲斯特电力科技有限公司 | 滤波器 |
CN107004516A (zh) * | 2014-11-03 | 2017-08-01 | 哈金森公司 | 导电电极及其制造方法 |
WO2024020724A1 (zh) * | 2022-07-25 | 2024-02-01 | 宁德时代新能源科技股份有限公司 | 电极浆料、电极极片及其制备方法、二次电池和用电装置 |
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JP2002025340A (ja) * | 2000-07-04 | 2002-01-25 | Nisshinbo Ind Inc | 導電性樹脂組成物、燃料電池セパレータ及びその製造方法並びに固体高分子型燃料電池 |
US20030008209A1 (en) * | 2001-06-22 | 2003-01-09 | Marufur Rahim | Cathode coating dispersion |
EP1311017B1 (en) * | 2001-11-12 | 2008-10-15 | Matsushita Electric Industrial Co., Ltd. | Alkaline storage battery |
JP4049321B2 (ja) * | 2001-11-21 | 2008-02-20 | 日立粉末冶金株式会社 | 燃料電池セパレーター用塗料 |
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JP6028286B2 (ja) * | 2011-10-24 | 2016-11-16 | 東洋インキScホールディングス株式会社 | 二次電池電極形成用エマルションバインダー、二次電池電極形成用合材インキ、二次電池電極、及び二次電池 |
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KR20230009096A (ko) * | 2021-07-08 | 2023-01-17 | 주식회사 엘지에너지솔루션 | 리튬 이차전지용 양극 슬러리 조성물, 양극 및 이를 포함하는 리튬 이차전지 |
KR20230009097A (ko) * | 2021-07-08 | 2023-01-17 | 주식회사 엘지에너지솔루션 | 리튬 이차전지용 양극 슬러리 조성물, 양극 및 이를 포함하는 리튬 이차전지 |
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BR0011187A (pt) * | 1999-04-14 | 2002-03-05 | Du Pont | Composição, artigo e processo de revestimento |
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JP3696762B2 (ja) * | 1999-09-30 | 2005-09-21 | 日立粉末冶金株式会社 | アルカリ電池正極缶用導電塗料 |
US6395459B1 (en) * | 2000-09-29 | 2002-05-28 | Eastman Kodak Company | Method of forming a protective overcoat for imaged elements and related articles |
US6572790B2 (en) * | 2001-01-09 | 2003-06-03 | National Starch And Chemical Investment Holding Corporation | Cathode coating dispersion |
US20030008209A1 (en) * | 2001-06-22 | 2003-01-09 | Marufur Rahim | Cathode coating dispersion |
-
2001
- 2001-06-22 US US09/888,306 patent/US20030008209A1/en not_active Abandoned
-
2002
- 2002-06-17 KR KR1020020033676A patent/KR20030001263A/ko not_active Application Discontinuation
- 2002-06-17 EP EP02013501A patent/EP1271671B1/en not_active Expired - Lifetime
- 2002-06-17 CA CA2390804A patent/CA2390804C/en not_active Expired - Fee Related
- 2002-06-17 AT AT02013501T patent/ATE529905T1/de not_active IP Right Cessation
- 2002-06-17 PT PT02013501T patent/PT1271671E/pt unknown
- 2002-06-20 JP JP2002179918A patent/JP4779066B2/ja not_active Expired - Fee Related
- 2002-06-20 SG SG200203762A patent/SG106074A1/en unknown
- 2002-06-21 CN CN02124863A patent/CN1393496A/zh active Pending
Cited By (7)
Publication number | Priority date | Publication date | Assignee | Title |
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CN101125972B (zh) * | 2007-09-12 | 2010-05-26 | 浙江大学宁波理工学院 | 规模化生产的超级电容器导电涂料及其工艺方法 |
CN104247112A (zh) * | 2012-04-13 | 2014-12-24 | 株式会社Uacj | 集电体、电极结构体、非水电解质电池及蓄电零部件 |
CN107004516A (zh) * | 2014-11-03 | 2017-08-01 | 哈金森公司 | 导电电极及其制造方法 |
CN111785528A (zh) * | 2014-11-03 | 2020-10-16 | 哈金森公司 | 导电电极及其制造方法 |
CN111785528B (zh) * | 2014-11-03 | 2022-02-15 | 哈金森公司 | 导电电极及其制造方法 |
CN105255287A (zh) * | 2015-11-20 | 2016-01-20 | 苏州菲斯特电力科技有限公司 | 滤波器 |
WO2024020724A1 (zh) * | 2022-07-25 | 2024-02-01 | 宁德时代新能源科技股份有限公司 | 电极浆料、电极极片及其制备方法、二次电池和用电装置 |
Also Published As
Publication number | Publication date |
---|---|
CA2390804A1 (en) | 2002-12-22 |
ATE529905T1 (de) | 2011-11-15 |
JP2003142105A (ja) | 2003-05-16 |
US20030008209A1 (en) | 2003-01-09 |
PT1271671E (pt) | 2012-01-10 |
EP1271671B1 (en) | 2011-10-19 |
EP1271671A1 (en) | 2003-01-02 |
KR20030001263A (ko) | 2003-01-06 |
CA2390804C (en) | 2014-05-20 |
JP4779066B2 (ja) | 2011-09-21 |
SG106074A1 (en) | 2004-09-30 |
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